Hydroxy alkylene ethers of divinyl glycol

ABSTRACT

A novel polyalkylene glycol has the general formula   IN WHICH Z is an integer of 1, X + Y is an integer of from 1 to about 50 and R and R&#39;&#39; are radicals selected from the group consisting of hydrogen, a C1-C6alkyl, a C2-C6 alkenyl a C2-C6 alkynyl, and, when R and R&#39;&#39; are taken together, a C3-C6 alkylene. When X is an integer of O, the hydroxyl radical is linked directly to the carbon of unit Z of the formula and when Y is an integer of O, the hydrogen radical is linked directly to the oxygen of unit Z. It is preferred to have X and Y each being an integer of at least 1 and R and R&#39;&#39; be hydrogen or C1-C6 alkyl radicals or to represent, when taken together a C3-C6 alkylene radical. The polyalkylene glycols of this invention are produced by heating, in the presence of an alkaline catalyst, an epoxide of the general formula IN WHICH R and R&#39;&#39; have the same meaning as stated hereinabove, with divinyl glycol of the formula The epoxide is heated with the divinyl glycol at a temperature in the range from about 50* - 200* C. and the molar ratio of epoxide to divinyl glycol is between 1 and about 50.

United States Patent 1 Bader et a1.

45l Jan. 30, 1973 [54] HYDROXY ALKYLENE ETHERS OF DIVINYL GLYCOL [76]Inventors: Andre Bader, 150 avenue A. Maes; Francis Weiss, 3 Chemin duGrand Perron, both of Pierre-Benite, France [22] Filed: Jan. 9, 1970[21] Appl. No.: 1,860

Related US. Application Data [63] Continuation-in-part of Ser. No.686,763, Nov. 29,

1967, abandoned.

[52] US. Cl ..260/61l B, 260/611 R, 260/615 R, 260/615 B, 260/775 AP[51] Int. Cl ..C07c 43/14 [58] Field of Search.260/615 B, 615 R, 611 B,611 R [56] References Cited UNITED STATES PATENTS 2,445,379 7/1948 Younget a1 ..260/615 R X 1,971,662 8/1934 Schmidt et al. ..260/615 B X2,692,256 10/1954 Baver et a1. ..260/615 B 2,729,623 1/1956 Gregg..260/615 B X 3,042,725 7/1962 Carter et a1. ..260/615 B 3,261,8197/1966 Stogryn et a1. ..260/615 B 3,370,056 2/1968 Yotsuzuka et a1..260/6l5 B X FOREIGN PATENTS OR APPLICATIONS 1,205,618 9/1970 GreatBritain ..260/615 R Primary ExaminerBernard Helfin M Attorney-Pennie,Edmonds Morton, Taylor and Adams [57] ABSTRACT A novel polyalkyleneglycol has the general formula (3H2 R R H CH R R r l 1 1 r 1 HO L6H CHo-J L6H (IJH 0-l L6H 611-0 H in which Z is an integer of 1, X Y is aninteger of from 1 to about 50 and R and R are radicals selected from thegroup consisting of hydrogen, a C -C alkyl, a C C alkenyl a C C alkynyl,and, when R and R are taken together, a C C alkylene. When X is aninteger of O, the hydroxyl radical is linked directly to the carbon ofunit Z of the formula and when Y is an integer of O, the hydrogenradical is linked directly to the oxygen of unit Z. It is preferred tohave X and Y each being an integer of at least 1 and R and R be hydrogenor C,C alkyl radicals or to represent, when taken together a C -Calkylene radical. The polyalkylene glycols of this invention areproduced by heating, in the presence of an alkaline catalyst, an epoxideof the general formula R-CgOH-R in which R and R have the same meaningas stated hereinabove, with divinyl glycol of the formula 1 Claim, N0Drawings HYDROXY ALKYLENE ETHERS OF DIVINYL GLYCOL CROSS REFERENCE TORELATED APPLICATION This application is a continuation in part of ourpreviously filed application Ser. No. 686,763, filed Nov. 29, 1967, nowabandoned.

BACKGROUND OF THE INVENTION I. Field of the Invention This inventionrelates to the production of novel polyalkylene glycols. In particular,it relates to the production of these glycols by heating, in thepresence of an alkaline catalyst, an epoxide and a divinyl glycol.

II. Description of the Prior Art The divinyl-1,2 ethylene-dioxystructural group CH=CH c11=e1r -o- H- H--O v which is included in thegeneral formula (I) of this invention, confers desirable properties onthese products and their derivatives by reason of its diallylic-diethercharacter. These products and their derivatives can be hardened byautoxidation by exposure to air, by heating, or by copolymerization witha vinyl monomer.

The utility of allylic ethers in respect of the foregoing is well known.See L. A. ONeill and R. A. Brett, J. Oil Chem. Assn. I965, 48, No. 11,pp. 1,025-1 ,042. These compounds were formerly produced from diolswhich were produced by the partial etherification of polyols withallylic alcohol or methallylic alcohol, as, for example, themonoallylethers of glycerol or of trimethanol- 1,1,1 propane, thediallylether of pentaerythritol, and the tetra-allylethers ofdipentaery-thritol or of sorbitol. These partial ethers are difficult toselectively prepare which makes it a burdensome task to obtain productstherefrom which have the desired diol characteristics. Furthermore, theautoxidation of compounds which are basically allylethers is accompaniedby degradation reactions with the formation of volatile products such asacrolein, in the case of the allylethers, or of methacrolein, in thecase of the methallylic ethers.

The products of this invention are diols or mixtures of diols which, byvirtue of the nature of their formation, are especially well adapted tosubsequent use in the manufacture of linear products of polycondensationor of poly-addition. The polyalkylene glycols of this invention havemany uses. For example, they may be used as diluent reactants fordessicant oils, alkyd resins or unsaturated linear polyesters. They mayalso be used as starting materials for polyesters, polyurethanes, orunsaturated polyethers and they may be used as varnishes which can bedried in air or hardened by heat.

SUMMARY OF'THE INVENTION The present invention is based on the discoverythat novel polyalkylene glycols can be produced by heating, in thepresence of an alkaline catalyst, an epoxide and divinyl glycol, at atemperature in the range from about 50 200 C., where the molar ratio ofepoxide to divinyl glycol is between i and about 50. Broadly stated,this invention comprises novel polyalkylene glycols, and a process formanufacturing the same, having the general formula in which Z is aninteger of 1, X Y is an integer of from 1 to about 50 and R and R areradicals selected from the group consisting of hydrogen, a C -C alkyl, aC -C alkenyl a C -C alkynyl, and, when R and R are taken together, a C-C alkylene. When X is an integer of O, the hydroxyl radical is linkeddirectly to the carbon of unit Z of the formula and when Y is an integerof O, the hydrogen radical is linked directly to the oxygen of unit Z.It is preferred to have X and Y each being an integer of at least 1 andR and R be hydrogen or C -C alkyl radicals or to represent, when takentogether a C -C alkylene radical. The polyalkylene glycols of thisinvention are produced by heating, in the presence of an alkalinecatalyst, an epoxide of the general formula in which R a'nd'ii' have thesame 5855713555 55563 hereinabove with a divinyl glycol of the formulaon H (III) The epoxide is heated with the divinyl glycol at atemperature in the range from about 50200 C. and the molar ratio ofepoxide to divinyl glycol is between 1 and about 50.

DESCRIPTION OF THE PREFERRED PRACTICE OF THE INVENTION The products ofthis invention are produced by heating a mixture of divinyl glycol (III)and one or more epoxides of the general formula (II) to a temperaturewhich is preferably in the range between about 5020O C. in the presenceof about 0.01 to 5 percent by weight, with respect to the mixture, of analkaline catalyst. Suitable alkaline catalysts may be selected fromamong the alkaline or alkaline earth metals, their oxides, hydroxides oralcoholates. Examples of suitable catalysts are: sodium, sodiumhydroxide, the methylate, ethylate or isopropylate of sodium, potassiumhydroxide, calcium oxide, or a strong organic base such as thequarternary hydroxide of ammonium and the hydroxide of benzyl trimethylammonium.

Among the epoxides of the general formula (II) which can be used in theprocess of this invention are, for example, ethylene oxide, propyleneoxide, epoxy- ],2 butane, epoxy-2,3 butane, and epoxy-3,4 butene-l andepoxy-1,2 cyclohexane the like cyclic epoxides. According to the givencircumstances and the fact that the reaction herein is exothermic, itmay be advantageous to add the epoxide (II) in an inert diluent such asa hydrocarbon or a solvent of the class comprising the ethers,diethylether, butylic ether, (C Hg) O, or dioxane.

The proportion of the epoxide (II) to be employed depends primarily onthe end result desired, since the molar ratio of epoxide to divinylglycol approximately determines the value of the index n of the productsof the invention. The molar ratio of epoxide to divinyl glycol can,therefore, take on values from I to about 50. There are generallyobtained from this reaction,

mixtures of diols having various chain length (X+Y+Z). These diolmixtures may be used without separation into their component fractionsof various chain length value. They may also be separated according toknown methods as, for example, by distillation, for the separation ofproducts of low molecular weight.

In general the reaction must be carried out in a closed vessel since thetemperature necessary to carry out the reaction within reasonableperiods of time, on the order of a few hours, is almost always higherthan the boiling point of the epoxides which are used as startingmaterials. Consequently, the process is carried out either under aself-generated supra-atmospheric pressure or one which may besupplemented or replaced by an inert gas such as nitrogen or hydrogen,the pressure amounting to from 1 to about 50 atmospheres.

The following non-limiting examples illustrate the process of producingthe novel polyalkylene glycols of this invention.

EXAMPLE 1 114 g. (1 mol) of divinyl glycol, 116 g. (2 mols) ofpropyleneoxide and 8 g. of an aqueous, 40 percent by weight solution, ofbenzyl-trimethyl ammonium hydroxide were placed into an autoclave. Afterpurging the atmosphere of the autoclave by means of nitrogen gas, apressure of approximately atmospheres of nitrogen was established withinthe autoclave and the mixture therein was heated for 6 hours at 80 C.The catalyst was then neutralized by the addition of a stoichiometricquantity of hydrochloric acid and the mixture was distilled at reducedpressure.

After the water and untransformed propylene oxide were removed byevaporation, there was recovered at a temperature of 93-110 C. and apressure of 0.5 mm. of mercury, 224 g. of a colorless liquid having theindices n 1.463 and d 1.009, titrating 0.95 equivalents of alcohol per100 g. by acetylation and having 0.82 double bonds per 100 g. bybromination. The yield was primarily composed of the products ofaddition of two units of propylene oxide to one mol of divinyl glycol.According to the theoretical, there should be 0.87 equivalents of bothalcohol and double bonds per 100 grams.

The ability of this product to produce an air hardening polyurethaneresin was then examined. A resin was prepared by mixing 21 g. of thisproduct, 10.8 g. of benzylic alcohol and 21.8 g. toluene diisocyanate.This mixture rose spontaneously in temperature to 60 C. There was thenadded 0.1 g. of quinoline and the resulting mixture was heated for ahalf hour at 90-100 C. After cooling there was obtained a solid productwhich was dissolved in an approximately equal weight of xylene. Into thesolution there was also dissolved 0.5 g. cobalt naphthenate. Thissolution was then spread on a glass plate by means of a brush. Thecoating dried and hardened in 4 hours, leaving a colorless transparentfilm adhering to the glass.

EXAMPLE 2 114 g. (1 mol) of divinyl glycol, 232 g. (4 mols) of propyleneoxide and 8 g. of an aqueous, 40 percent by weight solution, ofbenzyl-trimethyl ammonium hydroxide were placed in an autoclave, whichwas heated for 6 hours at a temperature of 80 C. under the pressureproduced by the reactants themselves. Thereafter the mixture wasneutralized and the untransformed propylene oxide was distilled off atatmospheric pressure. The water was then evaporated off at reducedpressure. There were obtained 204 g. of a product which was distilled at-79 C. and a pressure of 0.5 mm. of mercury. The distilled product was acolorless liquid having indices of u 1.465 and df= 1.023 and contained77 percent of the product of addition of one unit of propylene oxide to1 mol of divinyl glycol and approximately 23 percent of the product ofaddition of 2 units of propylene oxide to 1 mol of divinyl glycol(according to gas chromatography). This product also contained traces ofuntransformed divinyl glycol.

EXAMPLE 3 114 g. (1 mol) of divinyl glycol, 464 g. (8 mols) of propyleneoxide and 8 g. of a 30 percent by weight solution of aqueousbenzyl-trimethyl ammonium hydroxide were placed in an autoclave andheated for 6 hours at 80 C. under a pressure of approximately 20atmospheres produced by nitrogen. The mixture was then neutralized andthe untransformed propylene oxide was distilled off at atmosphericpressure. The water was then distilled off at reduced pressure. Therewere obtained 348 g. of a clear yellow liquid of d 1.007, titrating 0.63equivalents of hydroxy per g. and 0.56 equivalents double bonds per 100g.

The susceptibility to hardening by oxidation in air of a polyurethaneprepared by heating 31.5 g. of this polyether with 17.5 g. of toluenediisocyanate, in the presence of 50 mg. of quinoline was examined byexposure to air for an hour at 100 C. There was then prepared a 30percent solution of the solid polyurethane thus obtained incyclohexanone, to which solution there was added 0.1 percent of cobaltnaphthenate. This solution was spread on a glass plate. After two hoursthe result was a hard and adherent film.

EXAMPLE 4 114 g. (1 mol) of divinyl glycol, 1,160 g. (20 mols) ofpropylene oxide and 2.5 g. of metallic sodium were introduced into anautoclave and were maintained under a pressure of nitrogen amounting toapproximately 20 atmospheres. The mixture was then heated for 4 hours atC. The reaction mixture was then neutralized by addition of astoichiometric quantity of sulfuric acid and the untransformed propyleneoxide was then distilled off. The residue was then dried at 100 C. undera pressure of one mm. of mercury. There remained behind 745 g. of amixture of diols, slightly colored, having an index d 1.015,. andaccording to testing by acetylation, 0.23 OH per 100 g. and, bybromination, 0.19 double bonds per 100 g.

EXAMPLE 5 114 g. (1 mol) of divinyl glycol, 176 g. (4 mols) of ethyleneoxide and l g. of metallic sodium were placed in an autoclave and theremaintained under a pressure of nitrogen amounting to approximately 20atmospheres. The mixture was then heated for 6 hours at 80 C. Themixture of reactants was then neutralized, whereupon the volatilecomponents were evaporated with a gradually rising temperature, up to100 C., under a pressure of 0.1 mm. of mercury. There then remainedbehind 285 g. of a slightly viscous liquid product having an index (11.086, 0.65 equivalents hydroxy and 0.65 equivalents of double bonds per100 EXAMPLE 6 EXAMPLE 7 The method of any one of the previous examplesis followed except that the epoxide therein used is replaced separatelyand in turn by an equimolar amount of epoxy-1,2 butane, epoxy-2,3 butaneand epoxy-1,2 cyclohexane. In each suitable glycols are obtained.

WhTe the invention has been described hereinabove in terms of a numberof examples of the process 6 thereofl the invention itself is notlimited thereto, but rather comprehends all modifications of anddepartures from those examples properly falling within the spirit andscope of the appended claims.

In the foregoing examples the following symbols have the followingmeanings: n refers to the index of refraction of the compound, withreference to the sodium D line, at a temperature of 20 C.; (1 refers tothe specific gravity of the compound at 20 C. with reference to water ata temperature of 40 C.

What is claimed is:

1. A polyalkylene glycol of the general formula:

in which Z is an integer of 1, X Y is an integer of from 1 to about 50,when X is an integer ofO the HO radical is linked directly to the carbonof unit Z and when 'Y is an integer of 0 the H atom is linked directlyto the oxygen of unit Z, and R and R are selected from the groupconsisting of hydrogen, a C C alkyl, a C C alkenyl, a C C alkynyl, and,when R and R' are taken together, a C C alkylene.

